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Addition von Phosphanen an das Cα-Atom von Allenyliden(pentacarbonyl)chrom und Umlagerung in Phosphan-Komplexe

Addition von Phosphanen an das Cα-Atom von Allenyliden(pentacarbonyl)chrom und Umlagerung in Phosphan-Komplexe

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Prüfsumme: MD5:1007dc647ac1bea0e346614c3c7a61d6

FISCHER, Helmut, David REINDL, Carsten TROLL, Frédéric LEROUX, 1995. Addition von Phosphanen an das Cα-Atom von Allenyliden(pentacarbonyl)chrom und Umlagerung in Phosphan-Komplexe. In: Journal of Organometallic Chemistry. 490(1-2), pp. 221-227. ISSN 0022-328X. Available under: doi: 10.1016/0022-328X(94)05210-3

@article{Fischer1995Addit-23266, title={Addition von Phosphanen an das Cα-Atom von Allenyliden(pentacarbonyl)chrom und Umlagerung in Phosphan-Komplexe}, year={1995}, doi={10.1016/0022-328X(94)05210-3}, number={1-2}, volume={490}, issn={0022-328X}, journal={Journal of Organometallic Chemistry}, pages={221--227}, author={Fischer, Helmut and Reindl, David and Troll, Carsten and Leroux, Frédéric} }

eng 2013-06-26T09:24:33Z Addition von Phosphanen an das Cα-Atom von Allenyliden(pentacarbonyl)chrom und Umlagerung in Phosphan-Komplexe Leroux, Frédéric 2013-06-26T09:24:33Z Troll, Carsten Fischer, Helmut Reindl, David Journal of Organometallic Chemistry ; 490 (1995), 1-2. - S. 221-227 1995 Fischer, Helmut deposit-license The allenylidene(pentacarbonyl)chromium complex (CO)<sub>5</sub>Cr[C=C=C(C<sub>6</sub>H<sub>4</sub>NMe<sub>2</sub>-p)<sub>2</sub>] (1a) adds phosphines PR<sub>3</sub> at the C<sub>α</sub> atom to give ylide complexes, (CO)<sub>5</sub>Cr-[C(PR<sub>3</sub>=C=C(C<sub>6</sub>H<sub>4</sub>NMe<sub>2</sub>-p)<sub>2</sub>] (PR<sub>3</sub> = PMe<sub>3</sub> (3), PHPh<sub>2</sub> (3), PH<sub>2</sub>Mes (7) (Mes = C<sub>6</sub>H<sub>2</sub>Me3-2,4,6)). At room temperature complex 3 slowly rearranges to the allenylphosphine complex (CO)<sub>5</sub>Cr-PPh<sub>2</sub>[CH=C=C(C<sub>6</sub>H<sub>4</sub>NMe<sub>2</sub>-p)<sub>2</sub>] (4). The structure of 4 was established by an X-ray structure analysis. The adduct 7 obtained from 1a and PH<sub>2</sub>Mes, however, could not be detected. It immediately isomerizes to the alkynylphosphine complex (CO)<sub>5</sub>Cr-PH(Mes)[C≡C-CH(C<sub>6</sub>H<sub>4</sub>NMe<sub>2</sub>-p)<sub>2</sub>] (8). At room temperature the ylide complex 5, formed by addition of PHPh2 to the C<sub>α</sub> atom of the allenylidene complex (CO)<sub>5</sub>Cr=C=C=C(o-C<sub>6</sub>H<sub>4</sub>)<sub>2</sub>O (1b), rearranges in CH<sub>2</sub>Cl<sub>2</sub> in the presence of excess PHPh<sub>2</sub> to give a binuclear bisphosphine complex (6). 6 corresponds to the product of the chemo-, regio- and stereo-selective dimerization of the allenylphosphine complex analogous to 4. Reindl, David Troll, Carsten Leroux, Frédéric

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